Semiconductor device having nonvolatile memory and method of manufacturing thereof

ABSTRACT

Described is a semiconductor device having a silicon oxide (SiO 2 ) film into which nitrogen atoms, in a range between approximately 2×10 20  atoms/cm 3  or more and 2×10 21  atoms/cm 3  or less, are introduced, used as an insulator film in the semiconductor device. For example, the device can be a nonvolatile memory device, and the silicon oxide film can be used as an insulator film between, e.g., a floating gate electrode and control gate electrode of the nonvolatile memory device. Stable operations and a retention capability of a nonvolatile memory device are obtained even if the nonvolatile memory device is scaled. Moreover, a programming voltage can be lowered. Also described are methods of fabricating the semiconductor device.

BACKGROUND OF THE INVENTION

The present invention relates to a semiconductor device, particularly toan art to be effectively applied to a semiconductor device comprising anonvolatile memory device including an insulator film formed between afloating gate electrode and a control gate electrode. The presentinvention is especially directed to a nonvolatile memory (including,e.g., stacked type memories; or split type memories; or stacked typememories optionally having an erase gate in addition to the control andfloating gates; or split type memories optionally having an erase gatein addition to the control and floating gates, with insulator filmsbetween the various gates), such as a flash memory.

A semiconductor device uses a nonvolatile memory device referred to as aflash memory. Because the flash memory is superior in portability andimpact resistance and electrically allows on-board bulk erasing, it isanticipated as a file memory of a future compact portable data unit.

The flash memory is provided with a memory cell array sectionconstituted by arranging a plurality of memory cells using a nonvolatilememory device as a memory unit like a matrix. The nonvolatile memorydevice is constituted on the surface of a semiconductor substrate madeof, e.g., single crystalline silicon.

The above nonvolatile memory device mainly comprises a semiconductorsubstrate serving as a channel region, a first gate dielectric film, afloating gate electrode, a second gate dielectric film, a control gateelectrode, and a pair of semiconductor regions serving as a sourceregion and a drain region (also referred to as impurity diffusionlayers). The nonvolatile memory device injects electrons into thefloating gate electrode of the semiconductor substrate by applying apositive voltage to the control gate electrode of the semiconductorsubstrate, and stores one-bit data (“0” or “1”) in accordance with thedifference in the threshold voltages of memory cell transistors.Moreover, the first gate dielectric film denotes a tunnel dielectricfilm formed between the semiconductor substrate and the floating gateelectrode. Furthermore, the second gate dielectric film denotes, e.g.,an interpoly dielectric film formed between the floating gate electrodeand the control gate electrode.

In the case of the nonvolatile memory device, the floating gateelectrode and the control gate electrode are each respectively formedfrom a polycrystalline silicon film, and the first gate dielectric filmand the second gate dielectric film are respectively formed from asilicon oxide (SiO₂) film. A silicon oxide film serving as the firstgate dielectric film is formed by applying thermal oxidation to thesurface of a semiconductor substrate made of single crystalline silicon,and a silicon oxide film serving as the second gate dielectric film isformed by applying thermal oxidation to the surface of a floating gateelectrode made of a polycrystalline silicon film.

The silicon oxide film formed on the surface of the floating gateelectrode made of the polycrystalline silicon film has a low breakdownvoltage and is inferior in retention capability compared to a siliconoxide film formed on the surface of a semiconductor substrate made ofsingle-crystal silicon. Therefore, in the case of flash memories of 4[Mbit] onward, as the second gate dielectric film there is formed, inplace of the single-layer silicon oxide film, a composite film,so-called an ONO (Oxide/Nitride/Oxide) film, obtained by superimposing asilicon oxide film, a silicon nitride (Si₃N₄) film, and a silicon oxidefilm in order on the floating gate electrode. This is because, when filmthicknesses in terms of a silicon oxide film are the same, an ONO filmhas a small leakage current compared with a silicon oxide film. This artis discussed in “IEEE Transaction on Electron Devices, 38(1991) pp.386-391”.

SUMMARY OF THE INVENTION

However, as the integration of a flash memory is improved, new problemsoccur when using an ONO film as the second gate dielectric film. One ofthe problems is that the process temperature following scaling of anonvolatile memory device lowers. The ONO film is normally formed bythermally oxidizing the surface of a floating gate electrode made of apolycrystalline silicon film and thereby forming a lower silicon oxidefilm, then forming a silicon nitride film on the bottom silicon oxidefilm by a Low Pressure Chemical Vapor Deposition (LPCVD) process, andfinally thermally oxidizing the surface of the silicon nitride film andthereby forming a top silicon oxide film. However, because oxidation ofthe silicon nitride film requires a high temperature of 900° C. orhigher, it is difficult to form a shallow junction indispensable forscaling of an LSI (Large Scale Integrated Circuit), when forming asource region and a drain region and thereafter forming the second gatedielectric film, and this is a factor for interrupting improvement inthe integration of a flash memory.

According to only the thermal oxidation process described above, it ispossible to form a second gate dielectric film, of a single-layersilicon oxide film, even at a low temperature of approximately 800° C.However, this process has the problems that the thickness of a siliconoxide film decreases at the top end of the side wall of a floating gateelectrode as the oxidation temperature is lowered, concentration ofelectric fields becomes remarkable at this portion, and leakage currentincreases. Moreover, an art is proposed in which a single-layer siliconoxide film is formed at a low temperature of approximately 750° C. bythe LPCVD process, instead of the thermal oxidation process, to use thefilm as the second gate dielectric film of a nonvolatile memory device.By using the LPCVD process, it is possible to decrease the leakagecurrent of a silicon oxide film compared to the case of using thethermal oxidation process. However, the effect of the LPCVD process isnot enough and it is practically difficult to apply the process to anonvolatile memory device.

Another problem is to decrease the thickness of the second gatedielectric film. A voltage Vfg to be applied to a floating gateelectrode for the programming/erasing operation of a nonvolatile memorydevice is shown by the following expression (1).

[Numerical Formula 1]

Vfg=C ₂ Vcg/(C ₁ +C ₂)  (1)

In the above expression, Vcg denotes a voltage applied to a control gateelectrode, C₁ denotes the capacitance of a first gate dielectric film,and C₂ denotes the capacitance of a second gate dielectric film. Toefficiently supply the voltage, applied to the control gate electrode,to the floating gate electrode and lower a programming voltage, it iseffective to decrease the thickness of the second gate dielectric filmand increase C₂. However, a conventional ONO film has a problem thatelectric charges accumulated in a floating gate electrode leak to acontrol gate electrode, that is, retention failure is actualized ifthicknesses of top and bottom silicon oxide films are set to 5 nm orless. Moreover, to form the top silicon oxide film up to a thickness of5 nm, it is necessary to form a silicon nitride film with a thickness of10 nm or more in order to prevent the bottom polycrystalline siliconfilm, serving as a floating gate electrode, from oxidizing. Therefore,approximately 15 nm is a lower limit to the thickness of an ONO film interms of a silicon oxide film. Because it is presently difficult todecrease the thickness of a first gate dielectric film, it is expectedthat a new second-gate-dielectric-film forming process is developed.

It is an object of the present invention to provide a semiconductordevice (e.g., a nonvolatile memory device) having a gate dielectric filmwith a small leakage current at a low temperature, compared to aconventional ONO film, and having a stable operation and a sufficientretention capability even for smaller size (higher integration), and amethod of manufacturing this semiconductor device.

It is another object of the present invention to provide a semiconductordevice (e.g., a nonvolatile memory device, such as a flash memory)having two gate electrodes with an insulating film therebetween (e.g.,floating and control gate electrodes, with an insulating filmtherebetween), wherein this insulating film has only a small leakagecurrent, and a method of manufacturing this semiconductor device.

Moreover, it is another object of the present invention to provide anart making it possible to form a thin gate dielectric film compared tothe case of using a conventional ONO film, and lower a programmingvoltage.

The above problems are solved by using a silicon oxide film or acomposite film of a silicon oxide film and a silicon nitride film as asecond gate dielectric film and introducing nitrogen into the siliconoxide film so that the maximum nitrogen atomic concentration in thesilicon oxide film reaches approximately 2×10²⁰ atoms/cm³ or higher.Moreover, it is more preferable that the maximum nitrogen atomicconcentration in the silicon oxide film is approximately 2×10²¹atoms/cm³ or less. Furthermore, by setting the maximum hydrogen atomicconcentration in the silicon oxide film to 5×10²⁰ atoms/cm³ or less,better advantage is obtained.

A semiconductor device of the present invention is characterized byhaving a silicon oxide film between a first silicon film (e.g., firstpolycrystalline silicon film) and a second silicon film (e.g., secondpolycrystalline silicon film) above the first silicon film, introducingnitrogen into the silicon oxide film, and keeping the maximum nitrogenatomic concentration in the silicon oxide film at approximately 2×10²⁰atoms/cm³ or higher, preferably approximately 2×10²¹ atoms/cm³ or lower.When the semiconductor device has a nonvolatile memory device, the firstsilicon film can correspond to a floating gate electrode, the siliconoxide film can correspond to a second gate dielectric film, and thesecond silicon film can correspond to a control gate electrode. In thiscase, n-type impurities such as phosphorus (P) are generally introducedinto the first silicon film and the second silicon film respectively. Byusing the silicon oxide film as the second gate dielectric film, it ispossible to realize a film thickness of 15 nm or less which cannot berealized for a conventional ONO film.

The above silicon oxide film is formed, illustratively, by the LPCVDprocess using monosilane (SiH₄) and nitrogen monoxide (N₂O) as sourcegases. According to this process, it is possible to form a silicon oxidefilm at a low temperature of 700° C. to 800° C. As described above,however, it is difficult to use a silicon oxide film formed by the LPCVDprocess directly as the second gate dielectric film of a nonvolatilememory device. This is because the silicon oxide film has a largeleakage current, and, when a power supply is cut off and the nonvolatilememory device is left as it is after injecting electrons into a floatinggate electrode, electrons accumulated in the floating gate electrodeleak to a control gate electrode and resultingly retention failureoccurs. Moreover, because of a large leakage current, when injectingelectrons into the floating gate electrode to boost the threshold of thenonvolatile memory device, problems also occur that the injectedelectrons go out to the control electrode side, the threshold voltage isnot sufficiently boosted, and the writing and erasing threshold windowscannot be secured. As the result of our study, it is clarified that theleakage current of the silicon oxide film is caused by a defect referredto as an E′ center present in the silicon oxide film.

The E′ center is described in the article by Y. Kamigaki, et al.,“Reduced Poly-Si TFT Threshold Voltage Instability By High-TemperatureHydrogenation of a-Si-Like Spin Centers”, in the 33rd annual proceedingsreliability physics 1995, pages 12-17, the contents of which areincorporated herein by reference in their entirety. Briefly, the E′center is Si≡O₃; and this defect can be removed by annealing in thepresence of nitrogen, whereby the nitrogen is incorporated in thestructure to form N—Si≡O₃, to get rid of the E′ center.

Therefore, in the case of the present invention, a leakage current isdecreased by annealing a silicon oxide film in an NH₃ environment (e.g.,atmosphere) and terminating an E′ center at nitrogen atoms. The leakagecurrent of the silicon oxide film is dependent on the nitrogen atomicconcentration in the silicon oxide film. To decrease leakage current,control retention failure, and moreover secure a threshold voltagewindow, it is necessary to keep the maximum nitrogen atomicconcentration in the silicon oxide film at approximately 2×10²⁰atoms/cm³ or higher, preferably at 2×10²¹ atoms/cm³ or lower. In thiscase, less nitrogen atoms are present in a middle region of the siliconoxide film than those in the top and bottom regions of the film. Toobtain the above nitrogen atomic concentration, it is necessary toperform annealing in an NH₃ environment (e.g., atmosphere) in atemperature range of 750° C. to 900° C., preferably in a temperaturerange of 800° C. to 850° C. Therefore, it is possible to lower thetemperature of the gate dielectric film forming process compared to thecase of a conventional ONO film. Preferably, the annealing in anitrogen-containing environment (e.g., an ammonia atmosphere) is at amaximum temperature of 900° C.; at such temperature in, e.g., theammonia atmosphere, nitrogen can be incorporated in the silicon oxidefilm in a maximum amount of 2×10²¹ atoms/cm³. The preferred maximumnitrogen concentration takes into account the annealing temperature.

Moreover, by keeping the maximum hydrogen atomic concentration in thesilicon oxide film at 5×10²⁰ atoms/cm³ or lower, the present inventionbecomes more preferable. This is because hydrogen atoms present in thesilicon oxide film form electron traps. When hydrogen atoms are presentand a programming/erasing is performed, electrons are accumulated in asecond gate dielectric film and the electrons accumulated in the gatedielectric film are discharged to a control gate electrode because ofthe subsequent leaving state and resultingly, retention failure occurs.To decrease the hydrogen atoms described above, it is necessary toperform wet oxidation for a short time at 800° C. to 900° C., preferablyat 850° C.

Moreover, the present invention becomes preferable by controlling thenitrogen atomic concentration in a silicon oxide film so that theconcentration becomes lower in the top region of the silicon oxide film(adjacent the control gate electrode) than in the bottom region of thefilm. This nitrogen atom distribution is achieved by performing theabove wet oxidation.

The present invention is not restricted to semiconductor devices havinga nonvolatile memory device. For example, an advantage can be alsoobtained by applying the present invention to a semiconductor devicehaving an MOS (Metal Oxide Semiconductor) transistor using one of theabove first silicon film and second silicon film as an active layer andthe other of them as a gate electrode, and moreover, using the abovesilicon oxide film as a gate dielectric film (insulator film formedbetween the active layer and the gate electrode). The MOS transistorincludes a load MOS transistor used for a memory cell of an SRAM (StaticRandom Access Memory) and a switching MOS transistor used for a liquidcrystal display.

Furthermore, an advantage is obtained by applying the present inventionto a semiconductor device having a capacitor using the first siliconfilm as a bottom electrode, the second silicon film as a top electrode,and the silicon oxide film as a dielectric film.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a portion of the flash memory(semiconductor device) of the embodiment 1 of the present invention;

FIG. 2(a) to 2(c) are cross-sectional views for explaining a method forfabricating the flash memory in FIG. 1;

FIGS. 3(a) to 3(c) are cross-sectional views for explaining a method forfabricating the flash memory in FIG. 2;

FIG. 4 is an illustration showing the relation between electric fieldand leakage current of a silicon oxide film;

FIG. 5 is an illustration showing the relation between electric fieldand leakage current of a silicon oxide film;

FIG. 6 is an illustration showing nitrogen atomic concentrationdistributions in a silicon oxide film;

FIG. 7 is an illustration showing the relation between nitrogen atomicconcentration and leakage current in a silicon oxide film;

FIG. 8 is an illustration showing retention capability;

FIGS. 9(a) to 9(c) are cross-sectional views for explaining a method forfabricating the flash memory (semiconductor device) of the embodiment 2of the preset invention;

FIGS. 10(a) to 10(d) are cross-sectional views for explaining a methodfor fabricating the flash memory in FIGS. 9(a) to 9(c);

FIG. 11 is an illustration showing nitrogen-and hydrogen-concentrationdistributions in a silicon oxide film;

FIG. 12 is an illustration showing nitrogen-and hydrogen-concentrationdistributions in a silicon oxide film;

FIGS. 13(a) to 13(d) are cross-sectional views for explaining a methodfor fabricating the flash memory (semiconductor device) of theembodiment 3 of the present invention;

FIGS. 14(a) to 14(d) are cross-sectional views for explaining a methodfor fabricating the flash memory in FIGS. 13(a) to 13(d);

FIGS. 15(a) to 15(e) are cross-sectional views for explaining a methodfor fabricating the flash memory (semiconductor device) of theembodiment 4 of the present invention.

FIGS. 16(a) to 16(d) are cross-sectional views for explaining a methodfor fabricating the flash memory in FIGS. 15(a) to 15(e);

FIG. 17 is an illustration showing the relation between gate length andthreshold voltage;

FIGS. 18(a) to 18(c) are cross-sectional views for explaining a methodfor fabricating the semiconductor device of the embodiment 5 of thepresent invention;

FIGS. 19(a) to 19(d) are cross-sectional views for explaining a methodfor fabricating the semiconductor device in FIGS. 18(a) to 18(c); and

FIG. 20 is an illustration of threshold voltage change values due toprogramming/erasing before and after reduction of hydrogen atoms by wetoxidation.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Embodiments of the present invention are described below in detail byreferring to the accompanying drawings. These embodiments areillustrative of the present invention and not limiting thereof, thepresent invention being defined by the appended claims.

In every drawing for explaining the embodiments of the presentinvention, components having the same function are provided with thesame symbol, and their repetitive description is omitted.

Embodiment 1

For this embodiment, a case is described in which the present inventionis applied to an NOR-type flash memory as a semiconductor device havinga nonvolatile memory device.

FIG. 1 is a cross-sectional view of a portion of an NOR-type flashmemory.

The flash memory of this embodiment is provided with a memory cell arraysection in which a plurality of memory cells using the nonvolatilememory device Qe shown in FIG. 1 as one memory unit are arranged like amatrix.

The above flash memory mainly comprises a p-type semiconductor substrate201 made of single-crystal silicon and having a surface orientation(100). A field insulator film 202 is formed in the inactive region ofthe surface of the p-type semiconductor substrate 201 and a nonvolatilememory device Qe is constituted in the active region of the surface of ap-type semiconductor substrate 201 whose periphery (e.g., circumference)is specified by the field insulator film 202.

The nonvolatile memory device Qe mainly comprises the p-typesemiconductor substrate 201 used as a channel forming region, a firstgate dielectric film 203, a floating gate electrode 204, a second gatedielectric film 205, a control gate electrode 207, a punch-throughstopper region 208, a source region 209, and a drain region 210. In thiscase, the first gate dielectric film 203 represents a tunnel dielectricfilm formed between the p-type semiconductor substrate 201 and thefloating gate electrode 204. Moreover, the second gate dielectric film205 represents an interpoly dielectric film formed between the floatinggate electrode 204 and the control gate electrode 207.

The first gate dielectric film 203 is made of a silicon oxide filmformed by applying thermal oxidation to the surface of the p-typesemiconductor substrate 201. The floating gate electrode 204 is made ofa polycrystalline silicon film doped with n-type impurities in order todecrease the resistance value. The second gate dielectric film 205 ismade of a silicon oxide film formed by the LPCVD process using SiH₄ andN₂O as source gases. The silicon oxide film is doped with nitrogen inorder to decrease leakage current. The control gate electrode 207 ismade of a polycrystalline silicon film doped with n-type impurities inorder to decrease the resistance value.

The punch-through stopper region 208 comprises a p-type semiconductorregion containing p-type impurities introduced into the surface of thep-type semiconductor substrate 201. The source region 209 and the drainregion 210 comprise a pair of n-type semiconductor regions containingn-type impurities introduced into the surface of the p-typesemiconductor substrate 201.

An electrode 212 is electrically connected to the source region 209through a contact hole formed through an interlayer dielectric film 211,and moreover, the electrode 212 is electrically connected to the drainregion 210 through a contact hole formed through the interlayerdielectric film 211.

Then, a method for fabricating a memory cell using the nonvolatilememory device Qe as one memory unit is described below by referring toFIGS. 2(a)-2(c) and 3(a)-3(c) (cross-sectional views for explaining thefabrication method).

First, the p-type semiconductor substrate 201 made of single-crystalsilicon and having a surface orientation (100) is prepared. Then, thefield insulator film 202 made of a silicon oxide film is formed in theinactive region of the surface of the 15 p-type semiconductor substrate201 by the generally-known local oxidation. The field insulator film 202is formed at a thickness of approximately 500 nm. FIG. 2(a) shows theprocess up to this step for this embodiment.

Then, thermal oxidation is applied to the active region of the surfaceof the p-type semiconductor substrate 201 to form the first gatedielectric film 203 made of a silicon oxide film. The first gatedielectric film 203 is formed at a thickness of approximately 10 nm.

Then, the polycrystalline silicon film 204 doped with n-type impurities(e.g. phosphorus) is formed on the entire surface of the p-typesemiconductor substrate 201 including the surface of the first gatedielectric film 203. The polycrystalline silicon film 204 is formed at athickness of approximately 200 nm.

Then, patterning is applied to the polycrystalline silicon film 204. Thepatterning is performed by, e.g., standard photolithography and dryetching techniques. FIG. 2(b) shows the process up to this step.

Then, the silicon oxide film 205 is formed on the entire surface of thep-type semiconductor substrate 201 including the surface of thepolycrystalline silicon film 204 at a thickness of, for example, 12 nm.The silicon oxide film 205 is formed by the LPCVD process using SiH₄ andN₂O as source gases. In this case, the formation temperature is 750° C.

Then, annealing is performed in an NH₃ environment immediately after theabove steps are completed to dope the silicon oxide film 205 withnitrogen. FIG. 2(c) shows the process up to this step.

Then, the polycrystalline silicon film 207 doped with n-type impurities(e.g. phosphorus) is formed on the entire surface of the silicon oxidefilm 205. The polycrystalline silicon film 207 is formed at a thicknessof, for example, approximately 200 nm. FIG. 3(a) shows the process up tothis step.

Then, patterning for specifying the width in the gate-length directionis applied to the polycrystalline silicon film 207, silicon oxide film205, and polycrystalline silicon film 204, in order so as to form thecontrol gate electrode 207 made of the polycrystalline silicon film 207doped with n-type impurities, the second gate dielectric film 205 madeof the silicon oxide film doped with nitrogen, and the floating gateelectrode 204 made of the polycrystalline silicon film 204 doped withn-type impurities. The above electrodes and the film are patterned byphotolithography and dry etching techniques. In this process, though notillustrated, a word line integrated with the control gate electrode 207is also formed. FIG. 3(b) shows the process up to this step.

Then, the active region of the surface of the p-type semiconductorsubstrate 201 is locally doped with p-type impurities (e.g. boron) bythe ion implantation method to form the punch-through stopper region 208comprising a p-type semiconductor region.

Then, the active region of the surface of the p-type semiconductorsubstrate 201 is locally doped with n-type impurities (e.g. arsenic) bythe ion implantation method to form the source region 209 and drainregion 210 comprising a pair of n-type semiconductor regions. In thisprocess, a nonvolatile memory device Qe is formed. FIG. 3(c) shows theprocess up to this step.

Then, the interlayer dielectric film 211 is formed on the entire surfaceof the p-type semiconductor substrate 201 including the surface of thecontrol gate electrode 207. Thereafter, a contact hole reaching thesource region 209 and drain region 210 is formed on the interlayerdielectric film 211.

Then, a memory cell using the nonvolatile memory device Qe shown in FIG.1 as one memory unit is almost completed by forming a metallic film onthe entire surface of the interlayer dielectric film 211 including thecontact hole and thereafter patterning the metallic film to form theelectrodes 212.

Characteristics of the nonvolatile memory device Qe formed by the abovefabrication method are described below. In this case, samples made byvariously changing annealing temperatures and times in an NH₃environment were prepared to compare the nitrogen atomic concentrationand leakage current of the silicon oxide film (second gate dielectricfilm) 205 and characteristics of the nonvolatile memory device Qe.

FIGS. 4 and 5 show current-voltage characteristics of the silicon oxidefilm 205. FIG. 4 shows the result obtained by setting the annealingtemperature in an NH₃ environment to 850° C. and changing annealingtimes, and FIG. 5 shows the result obtained by setting the annealingtime to 10 min and changing annealing temperatures. The film thicknessis set to 12 nm in the both cases. In FIG. 4, curve 1 represents noannealing (prior art); and curves 2 and 3 respectively representannealing times of 10 minutes and 40 minutes (illustrating the presentinvention). In FIG. 5, curves 4, 5 and 6 respectively representannealing temperatures of 800° C., 850° C. and 900° C. From the resultsin FIGS. 4 and 5, it is found that the leakage current of the siliconoxide film 205 decreases as the annealing time and temperature in theNH₃ environment increase.

The leakage current decrease described above has a close correlationwith the nitrogen atomic concentration of the silicon oxide film 205.FIG. 6 shows the result of measuring the nitrogen atom distributions inthe ranges of the control gate electrode (polycrystalline silicon film207), second gate dielectric film (silicon oxide film 205), and floatinggate electrode (polycrystalline silicon film 204) by a secondary ionmass spectrometer (SIMS). Curve 7 represents nitrogen atom distributionwithout annealing (prior art), while curves 8 and 9 represent nitrogenatom distributions respectively with annealing times of 10 minutes and40 minutes.

From the annealing in the NH₃ environment, it is found that nitrogenatoms of 2×10²⁰ atoms/cm³ or more are introduced into the silicon oxidefilm 205. The nitrogen atomic concentration of the silicon oxide film205 is higher in the top and bottom regions than in the middle region.Moreover, it is found that the nitrogen atomic concentration rises asthe annealing time in the NH₃ environment increases.

FIG. 7 shows the relation between nitrogen atomic concentration andleakage current of the silicon oxide film 205 when annealing the film205 at various temperatures and times. In this case, the nitrogen atomicconcentration of the silicon oxide film 205 uses the value at the bottomregion of the film 205. The leakage current is defined by the maximumelectric field of 7.5 MV/cm applied to the second gate dielectric film205 when injecting electrons into the floating gate electrode 204. Fromthis result, it is found that the leakage current of the silicon oxidefilm 205 is dependent on the nitrogen atomic concentration of the film205 independently of any annealing condition, and it decreases as thenitrogen atomic concentration increases. To secure the threshold voltagewindow at the time of writing/erasing and maintain the retentioncharacteristic, it is necessary to decrease the leakage current of thesecond gate dielectric film 205 to 10⁻⁴ or less (the allowable leakagecurrent density, shown by curve 10 in FIG. 7). From FIG. 7, to realizethe above current level, it is necessary to increase the nitrogen atomicconcentration in the silicon oxide film 205 to 2×10²⁰ atoms/cm³ or more.

To fabricate a scaled nonvolatile memory device Qe having a gate lengthof 0.5 μm or less, it is necessary to set the upper limit of a processtemperature to 900° C. or lower. As the result of measuring the nitrogenatomic concentration in the silicon oxide film 205 on the samplesobtained by setting the annealing temperature of the film 205 in NH₃ to900° C. and changing the annealing times of the film 205 by theabove-described SIMS analysis, the concentration is saturated atapproximately 2×10²¹ atoms/cm³ and it is difficult to introduce morenitrogen atoms. Therefore, the nitrogen atomic concentration in thesilicon oxide film 205 is limited to a range between approximately2×10²⁰ atoms/cm³ or more and preferably 2×10²¹ atoms/cm³ or less (aregion for practical fabrication and use of the device-shown by arrow 11in FIG. 7).

FIG. 8 shows the change of threshold voltage when doping the siliconoxide film 205 with nitrogen atoms in an NH₃ environment for 10 min,injecting electrons into the floating gate electrode 204 of thenonvolatile memory device Qe, and thereafter performing baking in anitrogen environment at 250° C. FIG. 8 also shows the results of athermal silicon oxide film 12 and an ONO film 13 of the prior art, inaddition to those of the second gate dielectric film 205 (curve 14 inFIG. 8). Every film thickness is set to 12 nm.

It is found that the silicon oxide film 205 annealed in an NH₃environment has a small threshold-voltage drop compared to theconventional thermal silicon oxide film and ONO film, and the retentioncapability of the nonvolatile memory device Qe is improved. This is, asdescribed above, because the leakage current of the silicon oxide film205 decreases compared to the case of the thermal silicon oxide film andONO film when the thickness of the second gate dielectric film 205 isdecreased to 12 nm. If the nitrogen atomic concentration in the siliconoxide film 205 is kept in a range between approximately 2×10²⁰ atoms/cm³and preferably 2×10²¹ atoms/cm³ or less, the retention capability wasalmost the same.

According to this embodiment, by using the thermal silicon oxide film205 containing nitrogen atoms in a range between approximately 2×10²⁰atoms/cm³ or more and preferably 2×10²¹ atoms/cm³ or less as the secondgate dielectric film 205 of a nonvolatile memory device Qe, there is anadvantage that the retention capability is improved.

Embodiment 2

For this embodiment, a case is described in which a silicon oxide filmobtained by having the maximum nitrogen atomic concentration of the filmin a range between approximately 2×10²⁰ atoms/cm³ or more and preferably2×10²¹ atoms/cm³ or less, optimizing the nitrogen distribution, anddecreasing the hydrogen atomic concentration in the film, is used as thesecond gate dielectric film of a nonvolatile memory device.

First, a method for fabricating a memory cell using a nonvolatile memorydevice as one memory unit is described below by referring to FIGS. 9(a)to 9(c) and FIGS. 10(a) to 10(d) (cross-sectional views for explainingthe fabrication method).

A p-type semiconductor substrate 201 made of single-crystal silicon andhaving a surface orientation (100) is prepared, and then, a fieldinsulator film 202 made of a silicon oxide film is formed in theinactive region of the surface of the p-type semiconductor substrate 201by the generally-known local oxidation. The field insulator film 202 isformed at a thickness of approximately 500 nm. FIG. 9(a) shows theprocess up to this step for this embodiment.

Then, thermal oxidation is applied to the active region of the surfaceof the p-type semiconductor substrate 201 to form a first gatedielectric film 203 made of a silicon oxide film. The first gatedielectric film 203 is formed at a thickness of approximately 10 nm.

Then, a polycrystalline silicon film 204 doped with n-type impurities(e.g. phosphorus) is formed on the entire surface of the p-typesemiconductor substrate 201 including the surface of the first gatedielectric film 203. The polycrystalline silicon film 204 is formed at athickness of approximately 200 nm.

Then, patterning is applied to the polycrystalline silicon film 204.This patterning is performed by photolithography and the dry etchingtechniques. FIG. 9(b) shows the process up to this step.

Then, a silicon oxide film 205 is formed on the entire surface of thep-type semiconductor substrate 201 including the surface of thepolycrystalline silicon film 204 at a thickness of, for example, 12 nm.The silicon oxide film 205 is formed by the LPCVD process using SiH₄ andN₂O as source gases. In this case, the formation temperature is 750° C.

Then, annealing is performed in an NH₃ environment immediately after theabove step is executed to introduce nitrogen atoms of approximately6×10²⁰ atoms/cm³ into the silicon oxide film 205.

Then, wet oxidation is applied to the silicon oxide film 205 in anenvironment at a temperature of 825° C. FIG. 9(c) shows the process upto this 5 step.

Then, a polycrystalline silicon film 207 doped with n-type impurities(e.g. phosphorus) is formed on the entire surface of the silicon oxidefilm 205. The polycrystalline silicon film 207 is formed at a thicknessof approximately 200 nm. FIG. 10(a) shows the process up to this step.

Patterning for specifying the width in the gate length direction isapplied to the polycrystalline silicon film 207, silicon oxide film 205,and polycrystalline silicon film 204 in order so as to form a controlgate electrode 207 made of the polycrystalline silicon film 207 dopedwith n-type impurities, a second gate dielectric film 205 made of thesilicon oxide film 205 doped with nitrogen, and a floating gateelectrode 204 made of the polycrystalline silicon film 204 doped withn-type impurities. Patterning of these electrodes and film are performedby photolithography and dry etching techniques. In the above step,though not illustrated, a word line integrated with the control gateelectrode 207 is also formed. FIG. 10(b) shows the process up to thisstep.

Then, the active region of the surface of the p-type semiconductorsubstrate 201 is locally doped with p-type impurities (e.g. boron) bythe ion implantation method to form a punch-through stopper region 208comprising a p-type semiconductor region.

Then, the active region of the surface of the p-type semiconductorsubstrate 201 is locally doped with n-type impurities (e.g. arsenic) bythe ion implantation method to form a source region 209 and a drainregion 210 comprising a pair of n-type semiconductor regions. In thisstep, a nonvolatile memory device Qe is formed. FIG. 10(c) shows theprocess up to this step.

Then, an interlayer dielectric film 211 is formed on the entire surfaceof the p-type semiconductor substrate 201 including the surface of thecontrol gate electrode 207, and thereafter, contact holes reaching thesource region 209 and the drain region 210 are formed on the interlayerdielectric film 211.

Then, a metallic film is formed on the entire surface of the interlayerdielectric film 211 including the inside of the contact holes, andthereafter, patterned to form electrodes 212. Thus, as shown in FIG.10(d), a memory cell using a nonvolatile memory device Qe as one memoryunit is almost completed.

The nonvolatile memory device Qe of this embodiment can hold electriccharges for a long time compared to the case of the embodiment 1. Toexamine the reason for this, atomic-concentration distributions in thesilicon oxide film 205 before and after wet oxidation were observed by asecondary ion mass spectrometer.

FIG. 11 shows nitrogen- and hydrogen-concentration distributions in thesilicon oxide film 205 before wet oxidation and FIG. 12 shows nitrogen-and hydrogen-concentration distributions in the silicon oxide film 205after wet oxidation. In FIG. 11, curves 15 and 16 respectively showconcentrations of hydrogen and nitrogen in the silicon oxide film 205.In FIG. 12, curves 17 and 18 respectively show concentrations ofhydrogen and nitrogen in the silicon oxide film. As the result ofcomparing FIGS. 11 and 12, it is found that the hydrogen atomicconcentration in the silicon oxide film 205 decreases by one digit from2×10²¹ atoms/cm³ to 2×10²⁰ atoms/cm³. Moreover, it is confirmed that thenitrogen concentration in the top region (control gate electrode 207side) of the silicon oxide film 205 decreases. After annealing in thenitrogen-containing environment (atmosphere), but without performing thewet oxidation, a nitrogen concentration profile of the silicon oxidefilm would have three regions, first and third regions respectivelyadjacent the control and floating gate electrodes, and a second regionbetween the first and third region; the first and third regions wouldhave substantially a same concentration, while the second region wouldhave a reduced concentration relative to that of the first and thirdregions. After performing wet oxidation, the nitrogen concentration isreduced in the first region (i.e., adjacent the control gate electrode),but not in the third region; the nitrogen concentration in the thirdregion is then much greater than that in the first region. Thus, the wetoxidation has two beneficial effect: 1) reduces the hydrogenconcentration in the silicon oxide film; and 2) reduces nitrogenconcentration in the silicon oxide film in the region adjacent thecontrol gate electrode.

From the above analysis results, it is estimated that the reduction ofelectron traps due to reduction of hydrogen atoms in the silicon oxidefilm 205 and control of hole current due to reduction of the nitrogenconcentration in the top region (control gate electrode 207 side)improve the retention capability of the nonvolatile memory device Qe.

In the case of this embodiment, the nitrogen atomic concentration in thesilicon oxide film 205 is set to 6×10²⁰ atoms/cm³. However, it isobserved that the retention capability is improved when the nitrogenatomic concentration is kept in a range between approximately 2×10²⁰atoms/cm³ or more and preferably 2×10²¹ atoms/cm³ or less. Moreover,when the hydrogen atomic concentration in the silicon oxide film 205 iskept at 5×10²⁰ atoms/cm³ or less, the retention capability is alsoimproved. Furthermore, by setting the hydrogen atomic concentration inthe silicon oxide film 205 to 5×10²⁰ atoms/cm³ or less, it is possibleto control the threshold voltage change due to programming/erasing of anonvolatile memory device Qe. FIG. 20 shows threshold voltage changevalues due to programming/erasing before and after reduction of hydrogenatoms due to wet oxidation. In FIG. 20, curve 19 shows threshold voltagechange values before wet oxidation, and curve 20 shows threshold voltagechange values after wet oxidation. In this case, the nitrogen atomicconcentration is 6×10²⁰ atoms/cm³. Though the threshold voltage changeis 0.65 V before wet oxidation (hydrogen atomic concentration of 3×10²¹atoms/cm³), it is controlled to approximately 0.15 V after wet oxidation(hydrogen atomic concentration of 3×10²⁰ atoms/cm³). This is becauseelectron traps in the silicon oxide film 205 are reduced by reducinghydrogen atoms by wet oxidation.

Furthermore, in the case of this embodiment, the nitrogen atomicconcentration in the silicon oxide film 205 is set to 6×10²⁰ atoms/cm³.However, it is possible to control the threshold voltage change due toprogramming/erasing by keeping the nitrogen atomic concentration in arange between approximately 2×10²⁰ atoms/cm³ or more and preferably2×10²¹ atoms/cm³ or less and the hydrogen atomic concentration at 5×10²⁰atoms/cm³ or less.

This embodiment has an advantage that the retention capability of anonvolatile memory device Qe can be improved by using the silicon oxidefilm 205 containing nitrogen atoms in a range between approximately2×10²⁰ atoms/cm³ or more and preferably 2×10²¹ atoms/cm³ or less as thesecond gate dielectric film 205 of the nonvolatile memory device Qe,and, moreover, increasing the nitrogen atomic concentration in thebottom region of the silicon oxide film 205 compared to the nitrogenatomic concentration in the top region of the film 205 and setting themaximum hydrogen atomic concentration in the silicon oxide film 205 to5×10²⁰ atoms/cm³ or less. Moreover, the embodiment has an advantage thatthe threshold voltage change due to programming/erasing of thenonvolatile memory device Qe can be controlled.

Embodiment 3

For this embodiment, a silicon oxide film in which the maximum nitrogenatomic concentration is kept in a range between approximately 2×10²⁰atoms/cm³ or more and preferably 2×10²¹ atoms/cm³ or less, with asilicon nitride (Si₃N₄) film superimposed on the silicon oxide film,used as the second gate dielectric film of a nonvolatile memory device,is described.

First, a method for fabricating a memory cell using a nonvolatile memorydevice as one memory unit is described below by referring to FIGS. 13(a)to 13(d) and FIGS. 14(a) to 14(d) (cross-sectional views for explainingthe fabrication method).

A p-type semiconductor substrate 201 made of single-crystal silicon andhaving a surface orientation (100) is prepared, and then a fieldinsulator film 202 made of a silicon oxide film is formed in theinactive region of the surface of the p-type semiconductor substrate 201by the generally-known local oxidation. The field insulator film 202 isformed at a thickness of approximately 500 nm. FIG. 13(a) shows theprocess up to this step for this embodiment.

Then, thermal oxidation is applied to the active region of the surfaceof the p-type semiconductor substrate 201 to form a first gatedielectric film 203 made of a silicon oxide film. The first gatedielectric film 203 is formed at a thickness of approximately 10 nm.

Then, a polycrystalline silicon film 204 doped with n-type impurities(e.g. phosphorus) is formed on the entire surface of the p-typesemiconductor substrate 201 including the surface of the first gatedielectric film 203. The polycrystalline silicon film 204 is formed at athickness of approximately 200 nm.

Then, the polycrystalline silicon film 204 is patterned. This patterningis performed by photolithography and dry etching techniques. FIG. 13(b)shows the process up to this step.

Then, a silicon oxide film 205 is formed on the entire surface of thep-type semiconductor substrate 201 including the surface of thepolycrystalline silicon film 204 at a thickness of, for example, 12 nm.The silicon oxide film 205 is formed by the LPCVD process using SiH₄ andN₂O as source gases. In this case, the formation temperature is 750° C.

Then, annealing is performed in an NH₃ environment immediately after theabove step is performed to introduce nitrogen atoms of approximately6×10²⁰ atoms/cm³ into the silicon oxide film 205. FIG. 13(c) shows theprocess up to this step.

Then, a silicon nitride (Si₃N₄) film 213 (about 10 nm thickness) isformed on the entire surface of the p-type semiconductor substrate 201including the surface of the silicon oxide film 205 by the LPCVDprocess. FIG. 13(d) shows the process up to this step.

Then, a polycrystalline silicon film 207 doped with n-type impurities(e.g. phosphorus) is formed on the entire surface of the silicon oxidefilm 205. The polycrystalline silicon film 207 is formed at a thicknessof approximately 200 nm. FIG. 14(a) shows the process up to this step.

Then, patterning for specifying the width in the gate length directionis applied to the polycrystalline silicon film 207, silicon nitride film213, silicon oxide film 205, polycrystalline silicon film 204, and firstgate dielectric film 203 in order so as to form a control gate electrode207 made of the polycrystalline silicon film 207 doped with n-typeimpurities, a second gate dielectric film made of the silicon oxide film205 doped with nitrogen and the silicon nitride film 213, and a floatinggate electrode 204 made of the polycrystalline silicon film 204 dopedwith n-type impurities.

The above electrodes and film are patterned by photolithography and dryetching techniques. In the above step, though not illustrated, a wordline integrated with the control gate electrode 207 is also formed. FIG.14(b) shows the process up to this step.

Then, the active region of the surface of the p-type semiconductorsubstrate 201 is locally doped with p-type impurities (e.g. boron) bythe ion implantation method to form a punch-through stopper region 208comprising a p-type semiconductor region.

Then, the active region of the surface of the p-type semiconductorsubstrate 201 is locally doped with n-type impurities (e.g. arsenic) bythe ion implantation method to form a source region 209 and a drainregion 210 comprising a pair of n-type semiconductor regions. In thisstep, a nonvolatile memory device Qe is formed. FIG. 14(c) shows theprocess up to this step.

Then, an interlayer dielectric film 211 is formed on the entire surfaceof the p-type semiconductor substrate 201 including the surface of thecontrol gate electrode 207, and thereafter, contact holes reaching thesource region 209 and drain region 210 are formed through the interlayerdielectric film 211.

Then, a metallic film is formed on the entire surface of the interlayerdielectric film 211 including the inside of the contact holes, andthereafter, patterned to form electrodes 212. Thus, as shown in FIG.14(d), a memory cell using a nonvolatile memory device Qe as one memoryunit is almost completed.

The retention capability of the nonvolatile memory device Qe is improvedcompared to the case of depositing a silicon nitride film on an ONO filmwith a thickness of 12 nm.

In the case of this embodiment, the nitrogen atomic concentration in thesilicon oxide film 205 is set to 6×10²⁰ atoms/cm³ or more. However, whenthe concentration is kept in a range between approximately 2×10²⁰atoms/cm³ and preferably 2×10²¹ atoms/cm³ or less, improvement of theretention capability is observed.

This embodiment has an advantage that the retention capability of anonvolatile memory device Qe can be improved by using, as the secondgate dielectric film of the nonvolatile memory device Qe, the siliconoxide film 205 including nitrogen atoms in a range between approximately2×10²⁰ atoms/cm³ or more and 2×10²¹ atoms/cm³ or less and having thesilicon nitride film 213 superimposed on the silicon oxide film 205.

Moreover, in the case of this embodiment, nitrogen atoms are introducedinto the silicon oxide film 205, and, thereafter, the silicon nitridefilm 213 is formed. However, more advantages can be obtained byperforming wet oxidation similarly to the case of the embodiment 2before forming the silicon nitride film 213 and reducing the hydrogenatomic concentration in the silicon oxide film 205 to 5×10²⁰ atoms/cm³or less.

Embodiment 4

For this embodiment, a case is described in which a silicon oxide filmin which the maximum nitrogen atomic concentration is kept in a rangebetween approximately 2×10²⁰ atoms/cm³ or more and preferably 2×10²¹atoms/cm³ or less is used as the second gate dielectric film of anonvolatile memory device. The nonvolatile memory device of thisembodiment is mounted as a flash memory having an AND-type contactlessarray structure.

First, a method for fabricating a memory cell using a nonvolatile memorydevice as one memory unit is described below by referring to FIGS. 15(a)to 15(e) and FIGS. 16(a) to 16(d) (cross-sectional views for explainingthe fabrication method).

A p-type semiconductor substrate 101 made of single-crystal silicon andhaving a surface orientation (100) is prepared.

Then, a first gate dielectric film 102 made of a silicon oxide film isformed on the surface of the p-type semiconductor substrate 101.

Then, a polycrystalline silicon film 103 doped with impurities (e.g.phosphorus) is formed on the first gate dielectric film 102, and,thereafter, a silicon oxide film 104 is formed on the polycrystallinesilicon film 103 and then a silicon nitride film 105 is formed on thesilicon oxide film 104. The polycrystalline silicon film 103, siliconoxide film 104, and silicon nitride film 105 are formed in order by theLPCVD process.

Then, patterning for specifying the width in the gate length directionis applied to the silicon nitride film 105, silicon oxide film 104,polycrystalline silicon film 103, and first gate dielectric film 102.The patterning is performed by photolithography and dry etchingtechniques. FIG. 15(a) shows the process up to this step.

Then, a silicon nitride film is formed on the entire surface of thep-type semiconductor substrate 101, including the surface of the siliconnitride film 105, by the LPCVD process, and thereafter, anisotropic dryetching is applied to the silicon nitride film to form a sidewall spacer106. FIG. 15(b) shows the process up to this step.

Then, wet oxidation is performed to form a field insulator film 107 madeof a silicon oxide film on the surface of the p-type semiconductorsubstrate 101. The field insulator film 107 separates active regions(device forming regions). FIG. 15(c) shows the process up to this step.

Then, a hot phosphoric acid treatment is performed to remove the siliconnitride film 105 and sidewall spacer 106, and then, the active region ofthe surface of the p-type semiconductor substrate 101 is locally dopedwith p-type impurities (e.g. boron) by the ion implantation method toform a punch-through stopper region 108 comprising a p-typesemiconductor region.

Then, the active region of the surface of the p-type semiconductorsubstrate 101 is locally doped with n-type impurities (e.g. arsenic) bythe ion implantation method to form a source region 109 and a drainregion 110 comprising a pair of n-type semiconductor regions. FIG. 15(d)shows the process up to this step.

Then, a silicon oxide film 111 is formed on the entire surface of thep-type semiconductor substrate 101 including the surface of the siliconoxide film 104 by the LPCVD process, and thereafter, anisotropic etchingis applied to the silicon oxide film 111 until the upside of thepolycrystalline silicon film 103 is exposed. FIG. 15(e) shows theprocess up to this step.

Then, a polycrystalline silicon film 112 doped with n-type impurities(e.g. phosphorus) is formed on the entire surface of the p-typesemiconductor substrate 101 including the surface of the polycrystallinesilicon film 103, and thereafter, patterning for specifying the width inthe gate length direction is applied to the polycrystalline silicon film112. FIG. 16(a) shows the process up to this step.

Then, a silicon oxide film 113 is formed on the entire surface of thep-type semiconductor substrate 101 including the surface of thepolycrystalline silicon film 112 at a thickness of, for example, 12 nm.The silicon oxide film 113 is formed by the LPCVD process using SiH₄ andN₂O as source gases. In this case, the formation temperature is 750° C.

Then, annealing is performed in an NH₃ environment immediately after theabove step is performed to introduce nitrogen atoms of approximately6×10²⁰ atoms/cm³ into the silicon oxide film 113. FIG. 16(b) shows theprocess up to this step.

Then, a polycrystalline silicon film 115 doped with n-type impurities(e.g. phosphorus) is formed on the entire surface of the silicon oxidefilm 113.

Then, patterning for specifying the width in the gate width direction isapplied to the polycrystalline silicon film 115, silicon oxide film 113,polycrystalline silicon film 112, and polycrystalline silicon film 103in order so as to form a control gate electrode 115 made of thepolycrystalline silicon film 115 doped with n-type impurities, a secondgate dielectric film 113 made of the silicon oxide film 113 doped withnitrogen, and a floating gate electrode made of the polycrystallinesilicon films 112 and 103 doped with n-type impurities. The patterningof them is performed by photolithography and dry etching techniques. Inthis step, though not illustrated, a word line integrated with thecontrol gate electrode 115 is also formed. FIG. 16(c) shows the processup to this step.

Then, an interlayer dielectric film 116 is formed on the entire surfaceof the p-type semiconductor substrate 101 including the surface of thecontrol gate electrode 115, and thereafter, contact holes (though notillustrated in FIG. 16(d)) reaching the source region 109 and the drainregion 110 are formed through the interlayer dielectric film 116.

Then, a metallic film is formed on the entire surface of the interlayerdielectric film 116 including the inside of the contact holes, andthereafter, patterned to form electrodes 117. Thus, a memory cell usinga nonvolatile memory device Qe as one memory unit is almost completed.

The retention capability of the nonvolatile memory device Qe is improvedcompared to the case of using an ONO film with a thickness of 12 nm as asecond gate dielectric film. To obtain a preferable retention capabilitysimilarly to the case of the embodiment 1, it is necessary to keep thenitrogen atomic concentration in the silicon oxide film 113 in a rangebetween approximately 2×10²⁰ atoms/cm³ or more and preferably 2×10²¹atoms/cm³ or less.

Moreover, FIG. 17 shows the relation between gate length of thenonvolatile memory device using the silicon oxide film 113 as a secondgate dielectric film and threshold voltage of the nonvolatile memorydevice after ultraviolet light irradiation. In FIG. 17, curve 21represents the present invention, and curve 22 represents structureusing an ONO film (prior art) as a second gate dielectric film. Thesilicon oxide film annealed in an NH₃ environment can perform stableoperations even if the gate length is shorter than that of aconventional ONO film, for example, 0.3 μm or less. This is because thesilicon oxide film 113 has a formation temperature of 850° C. which islower than that of the ONO film, and thereby, the elongation of thesource and drain regions can be controlled.

This embodiment has an advantage that the retention capability can beimproved by using the silicon oxide film 113 containing nitrogen atomsin a range between approximately 2×10²⁰ atoms/cm³ or more and preferably2×10²¹ atoms/cm³ or less as the second gate dielectric film of thenonvolatile memory device Qe.

Moreover, there is an advantage that a scaled nonvolatile memory deviceQe can be stably operated by using a silicon oxide film in which themaximum nitrogen atomic concentration is kept in a range betweenapproximately 2×10²⁰ atoms/cm³ or more and preferably 2×10²¹ atoms/cm³or less as the second gate dielectric film of the nonvolatile memorydevice Qe, after forming source and drain regions.

Furthermore, in the case of this embodiment, nitrogen atoms areintroduced into the silicon oxide film 113 and thereafter thepolycrystalline silicon film 115 is formed. However, more advantages canbe obtained by performing wet oxidation before forming thepolycrystalline silicon film 115 similarly to the case of the embodiment2 and reducing the hydrogen atomic concentration in the silicon oxidefilm 114 to 5×10²⁰ atoms/cm³ or less.

Furthermore, as described in the embodiment 3, the same advantage can beobtained by forming a silicon nitride film and using a second gatedielectric film as a composite film before forming the polycrystallinesilicon film 115 after forming the silicon oxide film 113.

In the case of the embodiments 1 to 3, a nonvolatile memory device to bemounted as a NOR-type flash memory is described as an example. In thecase of the embodiment 4, a nonvolatile memory device to be mounted as aflash memory having an AND-type contactless array structure is describedas an example. Moreover, the same advantage can be obtained by applyingthe present invention to a nonvolatile memory device to be mounted asanother nonvolatile semiconductor memory such as the NAND type, DiNORtype, or split-gate type. In the case of the Embodiments 1-4, thesilicon oxide film in which the maximum nitrogen atomic concentration iskept in a range between approximately 2×10²⁰ atoms/cm³ or and preferablyat most 2×10²¹ atoms/cm³ is applied to the second gate dielectric filmbetween the floating gate electrode and control gate electrode. However,by keeping the concentration of nitrogen atoms in a range of at leastapproximately 2×10²⁰ atoms/cm³, and preferably at most 2×10²¹ atoms/cm³,the silicon oxide film can be applied to the interpoly dielectice filmbetween the floating gate electrode and the erase gate electrode.

Embodiment 5

For this embodiment, a case of using a silicon oxide film in which themaximum nitrogen atomic concentration is kept in a range betweenapproximately 2×10²⁰ atoms/cm³ or more and preferably 2×10²¹ atoms/cm³or less as the gate dielectric film of an MOS transistor using apolycrystalline silicon film as an active layer is described. In thecase of this embodiment, a gate dielectric film represents an insulatorfilm formed between the active layer and the gate electrode.

First, an MOS transistor fabrication method is described by referring toFIGS. 18(a) to 18(c) and FIGS. 19(a) to 19(d) (cross-sectional views forexplaining the fabrication method).

An n-type semiconductor substrate 301 made of single-crystal silicon andhaving a surface orientation (100) is prepared.

Then, a silicon oxide film 302 is formed on the surface of the n-typesemiconductor substrate 301. FIG. 18(a) shows the process up to thisstep.

Then, a polycrystalline silicon film 303 serving as the active layer ofan MOS transistor is formed on the silicon oxide film 302. FIG. 18(b)shows the process up to this step.

Then, a silicon oxide film 304 used as a gate dielectric film is formedon the polycrystalline silicon film 303 at a thickness of, for example,10 nm. The silicon oxide film 304 is formed by the LPCVD process usingSiH₄ and N₂O as source gases. In this case, the formation temperature is750° C.

Then, annealing is performed in an NH₃ environment immediately afterperforming the above step to introduce nitrogen atoms of approximately6×10²⁰ atoms/cm³ into the silicon oxide film 304. Thereafter, wetoxidation is performed in an environment at a temperature of 825° C. toreduce the hydrogen atomic concentration in the silicon oxide film 304to 5×10²⁰ atoms/cm³ or less. FIG. 18(c) shows the process up to thisstep.

Then, a polycrystalline silicon film 307 doped with p-type impurities(e.g. boron) is formed on the silicon oxide film 304. FIG. 19(a) showsthe process up to this step.

Then the polycrystalline silicon film 307 is patterned to form a gateelectrode made of the polycrystalline silicon film 307. The patterningis performed by photolithography and dry etching techniques. FIG. 19(b)shows the process up to this step.

Then, the polycrystalline silicon film 303 is doped with p-typeimpurities (e.g. boron) by the ion implantation method by using the gateelectrode 307 as an impurity doping mask to form a pair of p-typesemiconductor regions 308 serving as source and drain regions. In thisstep, an MOS transistor Q is formed. See FIG. 19(c).

Then, an interlayer dielectric film 309 is formed on the entire surfaceof the n-type semiconductor substrate 301 including the surface of thegate electrode 307, and thereafter, contact holes reaching the pair ofp-type semiconductor regions 308 are formed through the interlayerdielectric film 309.

Then, a metallic film is formed on the entire surface of the interlayerdielectric film including the inside of the contact holes, andthereafter, the metallic film is patterned to form a wiring 310.Thereby, the state shown in FIG. 19(d) is obtained.

The standby current of the MOS transistor is reduced compared to a caseof using a silicon oxide film formed by the CVD process or a siliconoxide film formed by thermally oxidizing the polycrystalline siliconfilm 303. Moreover, the on-current is increased. As a result, a highon/off ratio is obtained.

In the case of this embodiment, the nitrogen atomic concentration in thesilicon oxide film 304 is set to 6×10²⁰ atoms/cm³. However, by keepingthe concentration in a range between approximately 2×10²⁰ atoms/cm³ ormore and preferably 2×10²¹ atoms/cm³ or less, a high on/off ratio isalso obtained.

This embodiment has an advantage that the on/off ratio of an MOStransistor can be improved by using a silicon oxide film containingnitrogen atoms in a range between approximately 2×10²⁰ atoms/cm³ or moreand 2×10²¹ atoms/cm³ or less as the gate dielectric film of an MOStransistor using a polycrystalline silicon film as an active layer.

In the case of this embodiment, a p-channel conducting-type MOStransistor Q is described. However, the same advantage can be alsoobtained from an n-channel conducting-type MOS transistor.

Moreover, in the case of this embodiment, an MOS transistor using apolycrystalline silicon film as an active layer is formed by forming asilicon oxide film on a semiconductor substrate. However, the sameadvantage can be obtained by forming a polycrystalline silicon film on aglass substrate like a liquid-crystal-display driving MOS transistor(without a silicon single-crystal substrate).

Furthermore, in the case of this embodiment, an MOS transistor using abottom polycrystalline silicon film as an active layer and a toppolycrystalline silicon layer as a gate electrode is described. However,the same advantage can be also obtained from an MOS transistor using abottom polycrystalline silicon film as a gate electrode and a toppolycrystalline silicon film as an active layer.

In the case of the above embodiments 1 to 5, annealing is performed inan NH₃ environment when introducing nitrogen atoms into a silicon oxidefilm. However, it is also possible to use other gases containingnitrogen. For example, (and not to be limiting), the annealing can beperformed in environments containing at least one of N₂O, NO and NO₂,either in addition to or instead of NH₃. Differing rates and amounts ofincorporation of nitrogen occur with use of different gas environments;for example, N₂O and NO only have a small effect. Moreover, annealingtemperatures, to incorporate nitrogen in the silicon oxide film, varies;for example, annealing in an N₂O environment should be performed attemperatures greater than 900° C., and in an NO environment (at 1atmosphere pressure) the annealing temperature should be, e.g., around850° C.

Use of NH₃ has the advantage that the annealing to incorporate nitrogenin the silicon oxide film according to the present invention can beperformed at relatively low temperatures (e.g., where the pressure isaround one atmosphere, the annealing can be performed at around 700°C.). Accordingly, diffusion (enlargement) of active (impurity) regions,and degrading of the tunnel oxide, can be avoided. While use of an NH₃environment will also incorporate hydrogen in the silicon oxide filmduring the annealing, the concentration of hydrogen in the silicon oxidecan be reduced thereafter by the wet oxidation described previously.

Moreover, it is possible to introduce nitrogen atoms simultaneously withdeposition of a silicon oxide film. Furthermore, it is possible to useany other method as long as the advantages of the present invention canbe obtained.

Moreover, the above embodiments 1 to 5 are described by using apolycrystalline silicon film. However, the same advantage can beobtained from an amorphous silicon film.

The invention made by the present inventors is specifically describedabove in accordance with the above embodiments. However, the presentinvention is not restricted to the embodiments. It is a matter of coursethat various modifications can be made as long as they are not deviatedfrom the gist of the present invention.

For example, the present invention can be applied to a semiconductordevice having a capacitor using a bottom polycrystalline silicon film oran amorphous silicon film as a bottom electrode, a top polycrystallinesilicon film or an amorphous silicon film as a top electrode, and asilicon oxide film (having nitrogen incorporated therein according tothe present invention) between these electrodes as a dielectric film. Inthis case, the retention capability of the capacitor can be improved.

Moreover, the present invention can be applied to a one-chipmicrocomputer (semiconductor device) provided with a memory cell arrayhaving a nonvolatile memory device.

Advantages obtained from typical one of the inventions disclosed in thisapplication are briefly described below.

It is possible to improve the retention capability of a nonvolatilememory device to be mounted on a semiconductor device.

Moreover, it is possible to stably operate even a scaled nonvolatilememory device.

Furthermore, it is possible to reduce the programming voltage of anonvolatile memory device.

Furthermore, it is possible to improve the performances of an MOStransistor to be mounted on a semiconductor device.

Furthermore, it is possible to improve the retention capability of acapacitor to be mounted on a semiconductor device.

While we have shown and described several embodiments in accordance withthe present invention, it is understood that the same is not limitedthereto, but is susceptible to numerous changes and modifications asknown to one having ordinary skill in the art, and we therefore do notwish to be limited to the details shown and described herein, but intendto cover all such modifications as are encompassed by the scope of theappended claims.

We claim:
 1. A semiconductor device having a nonvolatile memory, thenonvolatile memory comprising a silicon oxide film formed between afirst silicon film which is a floating gate and a second silicon filmwhich is a control gate, the first silicon film overlying a substrate,the silicon oxide film having a thickness in a direction from the firstsilicon film to the second silicon film, and extends from adjacent thefirst silicon film to adjacent the second silicon film, the siliconoxide film having nitrogen included therein in an entirety of thethickness thereof, a maximum nitrogen concentration in the silicon oxidefilm being in a range from 2×10²⁰ atoms/cm³ to 2×10²¹ atoms/cm³, anitrogen concentration in the silicon oxide film having a peak at aregion adjacent the first silicon film, and decreasing, in saiddirection, toward the second silicon film.
 2. The semiconductor deviceaccording to claim 1, wherein the silicon oxide film has a hydrogenatomic concentration of at most 5×10²⁰ atoms/cm³.
 3. The semiconductordevice according to claim 1, wherein the first and second silicon filmsare each doped with n-type or p-type impurities so as to be conductive.4. The semiconductor device according to claim 1, wherein each of thefirst and second silicon films is made of amorphous silicon or ofpolycrystalline silicon.
 5. The semiconductor device according to claim1, wherein the silicon oxide film has a minimum nitrogen concentrationin a range from 2×10¹⁸ atoms/cm³ to 2×10²⁰ atoms/cm³.
 6. Thesemiconductor device according to claim 1, wherein the nitrogen is dopedin the silicon oxide film.
 7. The semiconductor device according toclaim 1, wherein the silicon oxide film has a thickness of less than 15nm.
 8. The semiconductor device according to claim 1, wherein thenitrogen concentration in the silicon oxide film adjacent the firstsilicon film, is greater than the nitrogen concentration in the siliconoxide film adjacent the second silicon film.
 9. A semiconductor devicehaving a nonvolatile memory, the nonvolatile memory comprising a siliconoxide film formed between a first silicon film which is a floating gateand a second silicon film which is a control gate, the first siliconfilm overlying a substrate, the silicon oxide film having a thickness ina direction from the first silicon film to the second silicon film, andextends from adjacent the first silicon film to adjacent the secondsilicon film, the silicon oxide film having nitrogen included therein inan entirety of the thickness thereof, the silicon oxide film having anitrogen concentration profile in the direction from the second siliconfilm to the first silicon film, the nitrogen concentration profilehaving a maximum adjacent the first silicon film, the nitrogenconcentration at the maximum adjacent the first silicon film being atleast 2×10²⁰ atoms/cm³, profile of the nitrogen concentrationdecreasing, in said direction, toward the second silicon film from themaximum adjacent the first silicon film.
 10. The semiconductor deviceaccording to claim 9, wherein the nitrogen concentration at the maximumadjacent the first silicon film is at most 2×10²¹ atoms/cm³.
 11. Thesemiconductor device according to claim 9, wherein the silicon oxidefilm has a maximum hydrogen atomic concentration of at most 5×10²⁰atoms/cm³.
 12. The semiconductor device according to claim 9, whereinthe first silicon film and the second silicon film each contains n-typeimpurities.
 13. The semiconductor device according to claim 9, whereineach of the first and second silicon films is made of amorphous siliconor of polycrystalline silicon.
 14. The semiconductor device according toclaim 9, wherein the silicon oxide film has a minimum nitrogenconcentration in a range from 2×10¹⁸ atoms/cm³ to 2×10²⁰ atoms/cm³. 15.The semiconductor device according to claim 9, wherein the nitrogenconcentration in the silicon oxide film adjacent the first silicon film,is greater than the nitrogen concentration in the silicon oxide filmadjacent the second silicon film.
 16. A semiconductor device having anonvolatile memory, the nonvolatile memory comprising a silicon oxidefilm between a first silicon film which is a floating gate and a secondsilicon film which is a control gate, the first silicon film overlying asubstrate, the silicon oxide film having a thickness in a direction fromthe first silicon film to the second silicon film, and extends fromadjacent the first silicon film to adjacent the second silicon film,wherein the silicon oxide film has a maximum hydrogen concentration of5×10²⁰ atoms/cm³, wherein the silicon oxide film has nitrogen includedtherein in an entirety of the thickness thereof, nitrogen being includedin the silicon oxide film in a maximum amount in a range of 2×10²⁰atoms/cm³ to 2×10²¹ atoms/cm³, wherein the silicon oxide film has anitrogen concentration profile in the direction from the first siliconfilm to the second silicon film, the nitrogen concentration profilehaving a maximum adjacent the first silicon film and decreasing, in saiddirection, from the first silicon film toward the second silicon film,and wherein each of the first and second silicon films is made ofamorphous silicon or of polycrystalline silicon.
 17. The semiconductordevice according to claim 16, wherein the silicon oxide film has aminimum nitrogen concentration in a range from 2×10¹⁸ atoms/cm³ to2×10²⁰ atoms/cm³.
 18. The semiconductor device according to claim 16,wherein the nitrogen is doped in the silicon oxide film.
 19. Thesemiconductor device according to claim 16, wherein the nitrogenconcentration in the silicon oxide film adjacent the first silicon film,is greater than the nitrogen concentration in the silicon oxide filmadjacent the second silicon film.
 20. A nonvolatile memory device havinga floating gate electrode, an insulating film and a control gateelectrode, manufactured by a method comprising the steps of: forming thefloating gate electrode, overlying a substrate; forming the insulatingfilm adjacent said floating gate electrode, the insulating film being asilicon oxide film formed by chemical vapor deposition, the siliconoxide film having a thickness in a direction extending perpendicularlyto the floating gate electrode, and away therefrom; annealing saidsilicon oxide film in a nitrogen-containing atmosphere to incorporatenitrogen in an entirety of the thickness of said silicon oxide film, amaximum amount of nitrogen included in the annealed silicon oxide filmbeing within a range of 2×10²⁰ to 2×10²¹ atoms/cm³; after the annealing,applying a wet oxidation to the silicon oxide film so as to reducehydrogen concentration in the silicon oxide film, wherein the wetoxidation is performed so as to reduce the hydrogen concentration to amaximum hydrogen concentration of at most 5×10²⁰ atoms/cm³ and todecrease nitrogen concentration in a region of the silicon oxide filmfurthest from the floating gate electrode, such that the nitrogenconcentration in the silicon oxide film decreases, in said direction,from the floating gate electrode through the silicon oxide film; andforming said control gate electrode adjacent said silicon oxide film,after the wet oxidation.
 21. The nonvolatile memory device according toclaim 20, wherein amount of nitrogen included in the silicon oxide filmin a region adjacent the floating gate electrode is greater than that ina region of the silicon oxide film adjacent the control gate electrode.